Tmoxanthone series and the proc-



Reissued Jan. 22, 1935 UNITED STATES PATENT OFFICE VAT DYESTUFFS lOFTHE ACRIDON'E AND THIOXANTHONE SERIES AND THE PROC- ESS OF MAKING THEM Paul Nawiasky,

Ludwigshafen-on-the-Rhine,

Wilhelm Bauer, Leverkusen; and Emil Krauch, Ludwigshafen-on-the-Bhine, Germany, aslign- I ors to General Analine Works, Inc. New .Iork. N. Y., a corporation of Delaware No Drawing. Original No. 1,898,458, dated February 21, 1933, Serial No. 506,490, January 3, 1931. Application for reissue September 14, 1934, SerialNo. 744,088. In Germany Janu- We have found that new and valuable vat dyestufls are obtained by converting acridoneor thioxanthone carboxylic acids or their derivatives into acid amides having the general formula:

in which A is an anthraquinone radicle, B and Y represent cyclic radicles and X represents NH or S and wherein, if X represents NH, the saidgroup CO.NHY must be attached to A. Dyestufis of this kind may be obtained for example by pre: paring, according to known methods, anthraquinoneacridoneor thioxanthone carboxylic acids which have the carboxyl group in the anthraquinone nucleus or anthraquinone thioxanthone carboxylic acids which have the carboxyl group in the part indicated by B in the above formula, the said acids (in the form of their halides) then being converted with amines in the manner already known into acid amides, Aninitia'l mate-' rial which is very suitable for the preparation of the new dyestuffs is the 1-nitroanthraquinone-6- carboxylic acid which is formed as the main product by the nitration of anthraquinone-Zwarboxylic acid in sulphuric acid monohydrate. The 1-nitroanthraquinone-6-carboxy1ic acid may for example be converted into l-aminoanthraquinone-G-carboxylic acid by reduction, or it may be converted into 1-chloranthraquinone-6-carboxylic acid by treatment with chlorine in organic solvents of high boiling point, and may then be converted by any known or suitable method into the corresponding anthraquinoneacridoneor thioxanthone carboxylic acids.

The dyestuffs obtainable according to the present invention are difflcultly soluble in organic solvents. They give colored solutions in concentrated sulphuric acid and form brown to dark-blue vats with alkaline hydrosulphite solutions;

The following examples will further illustrate the nature of this invention, butthe invention is not restricted to these examples. The parts are by weight. I j M Example 1 1.8 parts of 2,1(N) -anthraquinonebenzacridone-6-carboxylic acid chloride (obtainable from 1-chloranthraquinonea6 -carboxylic acid by conversion into the 'benzyl ester, condensation with anthranilic acid, ring closure with sulphuric acid and heating with thionyl chloride in trichlorbenzene) are heated to boiling with 1.2 parts of l-aminoanthraquinone in 40 parts of trichlorbenzene until the formation of dyestuff is completed. After cooling, the reaction mixture is I'll-- tered by suction, the dyestuff is purified by boiling up with about 300 parts of triehlorbenzene and if necessary crystallized from about 300 parts of trichlorbenzene. The dyestuif obtained which corresponds to the formula dyes cotton violet shades from a violet vat. The dyeings change to a fast red-brown in the air.

Example 2 2.4 parts of the chloride described in Example 1 are heated to boiling for a short time with 1.7

, parts of 1-amino-4-methoxyanthraquinone in 60 parts of trichlorbenzene. The dyestuif is worked up in a manner'similar to that described in Example I. It corresponds to the formula and dyes cotton powerful red-blown shades from a violet vat.

' Example 3 1. part of the chloridedescribed in Example 1 is heated to from-210'to 215 C. with 1 part of 1-amino-5-benzoylamino-anthraquinone in 20 parts of trichlorbenzene until the formation of dyestuff is completed. The dyestuff which separates out when the reaction mixture is cooled is preferably purified by boiling up with trichlorbenzene, vatting and allowing the vat to flow into chlorine liquor mula It corresponds to the for,-

and dyes cotton brown shedes fromaxred-riolet vat. --I-: -1.;".1. Example 4 example from l-chlor -anthraq non boxylic 'acid by; condensation with. thios ioylic acid, ring'clo'sur withsliliihuric' acid 'and treat? phorus' penta'chloride' is, heatedflto boiling tor short 'timejwith lifi phrts of aniline, The amlidov derivative which sebairates oi t in the cold filtered on by suction. git eg e pgndstolthefor,

mula

It dyes cotton violet shades sfrom a violet vat. The dyeings change toan oronge fast to chlorine 1-.4 .parts-otflAlS) -anthraquinonebenzthioxa,m thone-fi-carboxylic; acid chloride rarer heated to from about 210 to 215 C. in 20 parts of trichlorbenzene with 0.8 part of l-aminoanthraquinone until the formation of dyestuff is completed. The dyestufi which separates out on cooling is preferably purified by treatment with sodium hypochlorite. It corresponds to the formula.

and dyes reddish-.yellori from o. violetvat. V ,l

: 0mg? dWS fi i ta ns? s w-2 mennerpy employing amino compounds; other than. 'lf-ami t b uinone, T e tpm r 0f suchudyestufis are given in the follow- ":in'g'table:

. Condensation products of 2,1 (S) -anthmquinonebenzthioasanthone-G-carboxylic acid chloride un'thvamine s e i Molecular Z- proportions otamine to Color of" lmolecular V .vat

'' proportion of chloride Shade of dyeings Benzidine Violet 'pz'mige.

l amino 4 methoxy an- I thraquinone 1 l emiiio-F'benioyl-eim inoanthraquinone-;

Violet. Reddish-yellow.

1 Violet"; s amenello 1 .1mm 5 cmomimm quin'one...

Violet" 'Reddish-yellow.

I Red-brown.

3-fcarboxylic acid ethyl ester and i-chloran thrziquinonefli carboxylic 'acid benzyl ester, effecting ring closure by means of an alkaline s0- lfition' o1 hydrosulphite and converting the product intotheacid chloride by a treatment with thionylchlorideflfin trichlorbenze'nel are heated;

tojfboiling' for minutes with'flfl part of 1- a n iinoanthraquinonej in 60 "parts of trichlorbenzje The dyestuff separates from the warm r5 Q m ur iandlme be ed'af rsepare ionf by 'b'oilirig' it with trlchlorb'enzene'." It corresponds tothe form ila' I and dyes "cotter; fro'rnje "greenish Black va t the I s me shades which on exposureto the air change 40. parts of the chloride of 2,1] (N) -a,nthraquin one jfi-carboxylic 'acid' p p naphthacridone (obtaihable by condens'ationjoij 2-a'minonaphthalene- Example 7'- 3 parts of the initial material employed in Example 6 are heated to boiling for 10 minutes with 2.3 parts of o-amino--benzoylaminoanthraquinone in 160 parts of trichlorbenzene. The dyestufl is separated and purified as described in Example 6. It corresponds to theformula v and dyes cotton'green grey shadesfrom a vet having the same coloration, the shades changing to ayellowish olive on exposure to the air.

Example 8 404 parts of 2,1(S)-anthraquinonethioxan-' thone-Bz4-carboxylic acid chloride (obtainable by condensing 1-chloranthraquinone-2-carboxylic acid with p-mercaptobenzoic-acid, effecting ring closure by means of acetic anhydride with an addition 01f sulphuric acid and converting the ,product into the acid chloride by treatment with thionyl chloride in o-dichlorbenzene) are heated with 223 parts-of alpha eaminoanthraquinone in 12,600 parts of nitrobenzene to about 140 C. while stirring for 2 hours, whereby the mixture becomes thick, hydrogen chloride escapes and the dyestufi is separated. The mass is cooled to 80 C. and the dyestufi filtered off 'by suction. It is a yellow crystalline powder which is difficultly soluble in nitrobenzene even in the warm; It dissolves in concentrated sulphuric acid with the formation of an orange yellow solution. With alkaline hydrosulphite the dyestufi furnishes a violet black.

vat from which the vegetable fibre is dyed clear golden yellow shades of excellent fastness; The product corresponds to the formula Example 9 It in the process according to Example 8 o-mercaptobenzoic acid is used instead of p-mercaptobenzoic acid and resulting 2,1(S) -anthraquin-' onethioxanthone-Bz2-carbcxylic acid is condensed with 1-amino-5-benzcyIaminc-anthraquinone, a yellow dyestutt is obtained which dissolves in concentrated sulphuric acid to an orange yellow solution troni which it is" separated by the addition of'water in golden yellow flakes. With alkaline hydrosulphite 'the dyestufi forms a dark I v'iolet'v'at from which the vegetable fibre is dyed clear golden yellow shades. The product corresponds to the formula Example 10 If the 2,1(S) -anthraquinonethioxanthone-Bz2- carboxylic acid chloride used as initial material according to Example 9 is condensed with 1- amino-4 benzoylamino-anthraquinone, a dyestufi is obtained which dyes cotton from a violet vat orange red shades.

Example 11 4 parts of 3,2(S)-thioxanthoneanthraquinone- BZZ-carboxylic acid chloride (obtainable from 2- chlOr-B-anthraquirione carboxylic acid by condensation withthiosalicylic acid in aqueous solution withthe addition of caustic potash, effecting ring closure with concentrated sulphuric acid and converting the product into the carboxylic acid chloride byboiling withthionyl chloride in nitrobenzene) are heated with 2.3 parts of alpha-aminoanthraquinone in 180 parts of nitrobenzene to between 200" and 210 C. until hydrogen chloride is no longer evolved. After cooling, the yellow dyestuff which has separated out is filtered off by suction, washed and dried. With alkaline hydrosulphite the dyestuff yields a brownvat from which cotton is dyed clear greenish yellow shades, The product corresponds to the formula CO-HN Example 12" If the initial material used according to Example 11 is condensed with 3.4 partsof Lamina -V 5- benzoylamino-fanthraquinone, .a yellow. crystal line dyestufi is obtained whicliyields a brown vat with alkaline hydrosulphite, from which cotton is dyed clear golden yellow shades.

Example 13 2 parts of 1,2 (S) -anthraquinonethioxanthone- Bz2-carboxylic acid chloride (obtainable for example by condensing l-cyano-Z-bromo-anthraquinone with o-mercaptobenzoic acid, effecting saponification of the cyano group and simultaneous ring closure by means of sulphuric acid, and

converting the product into the acid chloride by heating with phosphorus pentachloride) are heated to between 180 and 190 C. with 1.7 parts of 1-amino-5-benzoylamino-anthraquinone in parts of nitrobenzene, until the formation of the dyestuff is complete. The resulting yellow dyestuff separates from the nitrobenzene while still hot; it is filtered off by suction and freed from nitrobenzene by washing with for example benzene. The dyestuff corresponds to the formula and dyes cotton from a greenish black vat greenish yellow shades. It dissolves in concentrated sulphuric acid with a yellowish brown coloration;

Example 14 4 parts of 4-amino-N-methyl-pyrimidoneanthrone are heatedto between 170 and C. with 2 parts of 2,l(S) -anthraquinone-thioxanthone-S-carboxylic acid chloride in 100 parts of nitrobenzene, until the formation of the d'yestuff is complete. The dyestuffseparates from the nitrobenzene while still hot; itis filtered off by suction and freed from nitrobe'n'zene by washing with for example benzene;

The'product corresponds to the formula It dissolves in concentrated sulphuric acid giving reddish orange solutions and dyes cotton from a violet vat orange shades.

What we claim is.'- l. Vat dyestuffs corresponding to. the general formula in which A indicates an anthraquinone radicle,

B and Y represent cyclic radicles and X represents NH or S and wherein, if X represents NH, the said group -CO--NHY must be attached to A, which dyestuffs are difiicultly soluble in organic solvents, give brown to dark-blue vats and give colored solutions in concentrated sulphuric acid.

2. Vat dyestufis corresponding to the general.

formula B CO-NH-Y and Y lndicates'an anthraquinone radiclej which dyestuffs are'difficultly soluble inorganic solvents; give brown to dark-blue vats and'give col ored solutions in concentrated sulphuric acid? 4; The'process of producing new vat dyestuffs which comprises condensing with a primary aromatic-amine a compound of'the general formula- 2a c0o1 o o which A indicates an anthraquinone radicle, B represents a benzene or naphthalene radicle, X indicates NH or S, and wherein, if X represents NH, the said group -CO- -Cl must be attached to A. A

5. The process of producing new vat dyestuffs which comprises condensing withan aminoanthraquinone a compound of the general formula in which A indicates an anthraquinone radicle, B represents a benzene or naphthalene radicle, X

' indicates NH or S, and wherein, if X represents NH, the said group COC1 must be to A.

6. The process of producing new vat dyestuffs which comprises condensing an anthraquinonethioxanthone-carboxylic acid chloride with an aminoanthraquinone.

'1. The process of producing new vat dyestuffs which comprises condensing an anthraquinonethioxanthone-carboxylic acid chloride with an aminoanthraquinone in an inert organic solvent.

attached 8., The process of producing a new vat dyestuff which comprises condensing 1,2(S) -anthraquinonethioxanthone-Bzil-rcarboxylic acid chloride with l-amino-5-benzoyl-amino-anthraquinone in nitrobenzene.

9. The vat dyestufi corresponding to the formula.

which dyestuflf dyes cotton from a greenish black vat greenish yellow shades and dissolves in concentrated sulphuric acid with a, yellowish brown coloration.

10. The vet dyestufi corresponding to the formula.

o G0--HN which dyestufi dyes cotton clear greenish yellow shades from a. brown vat.

PAUL NAWIASKY. WILHELM BAUER. EMIL KRAUCH. 

